Process for solution polymerization of acrylonitrile



3,323,333 Patented June 27, 1967 3,328,333 PRQCESS FOR SOLUTION POLYMERIZATION F ACRYLONITRILE Clarence C. Dannelly and John R. Caldwell, Kingsport,

Tenn, assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Fiied Oct. 23, 1965, Ser. No. 504,085 21 Claims. ((31. 260-30.4)

This application is a continuation-in-part of our copending application Ser. No. 270,143, filed April 3, 1963, and now abandoned.

This invention relates to a new and improved polymerization process for preparing resinous polymers of acrylonitrile. In one of its aspects this invention relates to the preparation of polyacrylonitrile and copolymers containing at least 50 percent by weight of acrylonitrile, employing a copper or ruthenium containing catalyst systern in an organic liquid which is a solvent for the polymer.

The problems and descriptions of the products of polymerization of acrylonitrile in solution with customary catalysts are discussed in several publications. For example, W. M. Thomas et al. have reported in Journal of Polymer Science, 17, 275 (1955), that the polymerization of acrylonitrile in ethlyene carbonate and in dimethylformamide, using azobis(butyronitrile) as the catalyst, resulted in polymer yields of 44 percent and 30 percent respectively, the latter process giving a product having an intrinsic viscosity of but 0.5. This result was attributed therein to the fact that interaction had occurred with the dimethylformarnide, i.e., chain transfer and retardation fully accounted for low reaction rates and the low molecular weights of the products obtained in dimethylformamide. As another example, British Patent No. 849,864 has proposed the use of ammonium persulfate as a single catalyst for polymerizing acrylonitrile in solution in dimethylformamide. However, it has been found that the process of this patent is not wholly satisfactory for commercial operation because of the necessity of using a temperature of 50 C. or above and for times in excess of 35 hours. The process of the invention does not have these limitations. The process of the invention actually gives better than 85 percent yield of polymer when using temperatures in the preferred range of about from 20-50 C., in a period of only from 2.5-4 hours. The polymer obtained is essentially colorless and the molecular weights are controllable and intrinsic viscosity values can be obtained, as desired, in the range of from 0.5-2.5. These important advantages of the process of the invention are believed to be due to the presence of both the metal or metal ions and the ozidizing agent.

Acrylonitrile has also been polymerized with free radical catalysts not including any metal or metal ion as a part of the polymerization catalyst. In some instances the catalysts have been in the form of multiple component systems such as the persulfate ion-bisulfite ion system in water. In other instances certain heavy metal ions such as copper have been used with persulfate or perphosphate ions as polymerization catalysts, but these catalysts have also been employed in water solutions at a particular pH. In those instances where homopolymers or copolymers of acrylonitrile have been prepared in solvents for the polymer, for example, dimethylsulfoxide, persulfates or ultraviolet light have been used to initiate the polymerization. Usually metals or metal ions have not been used to initiate the polymerization. Usually metals or metal ions have not been used in these catalyst systems and relatively low yields of polymer have been obtained. These low yields must be contrasted with the yields obtained in the practice of our invention which can be as high as 96% and higher based on the monomers being polymerized.

It is an object of this invention to provide an improved process for preparing acrylonitrile polymers in an organic liquid which is a solvent for the polymer. Another object is to provide a new catalyst combination for accelerating the polymerization reaction consisting of a copper containing catalyst in combination with a suitable oxidizing agent. Another object is to provide a new catalyst combination for accelerating the polymerization reaction consisting of a ruthenium containing catalyst in combination with a suitable oxidizing agent. Another object is to provide a solvent polymerization process for making acrylonitrile polymers that produces polymers having relatively high molecular weights, excellent color and low catalyst residues. Other objects will become apparent from the description and examples.

In accordance with the invention, the polymerizations of acrylonitrile alone or together with comonomer is carried out in a solution process, and the polymer can be extruded or spun directly from this solution without prior separation or recovery of the polymer from the reaction medium. One general method of practicing the invention consists of mixing or dissolving acrylonitrile monomer in organic liquids which are good solvents for polyacrylonitrile, for example, N,N-dirnethylformamide, N,N-dimethylacetamide, 'y-butyrolactone, ethylene carbonate and dimethylsulfoxide, as well as in various mixtures of these solvents with each other in any proportions and in mixtures of these solvents with up to 25 percent of other solvents such as lower alkanols, ketones, hydrocarbons and in particular acetonitrile. The relative proportion of monomer to solvent is advantageously in the range of from 5-60 percent by weight of acrylonitrile based on the total weight of the mixture. The usual and preferred range is from 10-40 percent by weight of monomer. The preferred solvent for the process of the invention is N,N- dimethylformamide, which produces very satisfactory polymer solutions of both polyacrylonitrile and the copolymers of acrylonitrile, for example, with alkyl acrylates and methacrylates. The catalyst which can be metallic copper in the form of a fine dispersion or in the form of various copper salts, e.g., copper salts of organic carboxylic acids such as cupric acetate, butyrate, etc., copper halides such as cupric chloride or bromide, copper nitrate, copper oxide or hydroxide, copper sulfate, etc. In place of copper catalysts we can use metallic ruthenium in the form of a fine dispersion or in the form of various salts of ruthenium, e.g., ruthenium chloride, ru thenium nitrate, ruthenium halides such as ruthenium chloride or bromide, ruthenium oxide or hydroxide, ruthenium sulfate etc. The salt need not be soluble in the mixture for the process to be operable. The useful range of catalyst is about from 0.00013.0 percent, preferably from 0001-10 percent, based on the weight of the monomet. This mixture is stirred under an inert atmosphere, for example, nitrogen and an oxidizing agent is added. The preferred oxidizing agents are the salts and acids of peroxysulfuric acid. These include Caros acid (H 0 or monoperoxysulfuric acid, peroxydisulfuric acid, the ammonium and alkali metal salts such as, for example, ammonium, potassium or sodium persulfate, etc., and sulfur tetroxide which, under certain conditions of low temperature and traces of Water, reacts to give a suitable oxidizing agent. However, the preferred specific oxidizing agent is potassium persulfate. In some instances, the oxidizing agent can advantageously be made in the reaction mixture, for example, using sulfuric acid and hydrogen peroxide to generate Caros acid. The quantity of the oxidizing agent used can be varied in accordance to the desired reaction rate, the characteristics of the oxidizing agent and the desired molecular weight of the resultant polymer. The desired range is based on the peroxy oxygen ('-O-O-) which is apparently available in the formulas of Cards acid and sulfodiperacid. The useful range of the oxidizing agent is about from 0.025-2.0 percent, based on the monomer weight.

The final mixture is then stirred under nitrogen at temperatures in the range of from 70 to 100 C., but preferably in the range of from 20-50 C. Depending on the temperature, the amount of catalyst used, and to a slight extent on the solvent a high yield of polyacrylonitrile forms in a period of from 0.5-24 hours. In the prefered temperature and catalyst ranges, the time for substantially complete polymerization of the monomer requires only about from 2.5-4 hours. Under some lowered temperature conditions, the newly former polymer may not be soluble as formed but dissolves on heating to normal temperatures; for example, if the polymerization is done in N,N-dimethylformamide below 30 C. The polymer readily dissolves on heating the mixture to 40 C. Depending on the solvent and the desired procedure, the solutions prepared as above described are then shaped into films or fibers by solvent evaporation or extraction using specific techniques known to the art.

In our process we obtain yields of at least 85% by weight of polymer based on the monomeric material charged to the process in 2 to 24 hours at temperatures of 50 to 50 C. The intrinsic viscosity of the polymer is within the range of 0.9-2.5 and the color of 0.005 inch thick film produced from the solution produced in our process is less than the color of a 0.5 inch layer of platinum cobalt chloride solution containing 500 p.p.m. of platinum.

Another method of practicing the process of the invention is to use the processes and materials described supra for the preparation of polyacrylonitrile to make useful copolymers of acrylonitrile. The only difference from the foregoing procedure is that the starting monomers for the process are mixtures of acrylonitrile and one or more other monoethylenically unsaturated, polymerizable compounds or comonomers containing a CII C group, and more especially a CH =C group. Suitable comonomers includes vinyl, isopropenyl and allyl esters of carboxylic acids containing from 27 carbon atoms, e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc., and the corresponding isopropenyl and allyl esters, allyl alcohol, alkyl acrylates and methacrylates wherein the alkyl group contains from 1-10 carbon atoms, e.g., methyl acrylate, ethyl acrylate, butyl acrylate, tertiary butyl acrylate, hexyl acrylate, decyl acrylate, etc., and the corresponding methacrylates, alicyclic acrylates and methacrylates wherein the alicyclic group contains from 5-8 or more carbon atoms, e.g., cyclopentyl acrylate, cyclohexyl acrylate, Z-norcamphanyl methacrylate, etc., vinyl halides, e.g., vinyl chloride, vinyl bromide and vinyl fluoride, vinylidene halides, e.g., vinylidene chloride, vinylidene bromide, vinylidene chloride-bromide, vinylidene fluoride, etc., acrylamide, methacrylamide, N-alkyl substituted acrylamides and methacrylami-des wherein the alkyl groups contain from 1-4 carbon atoms, e.g., N-methyl acrylamide, N-isopropylacrylamide, N-butylacrylamide, N,N- dimethylacrylamide, N,N-diisopropylacrylamide, etc., and the corresponding methacrylamides, methacrylonitrile, styrenes, e.g., styrene, ot-methylstyrene, a-acetoxystyrene, pmethylstyrene, p-acetaminostyrene, etc., vinyl pyridines, e.g., 2-vinylpyridine, 4-vinylpyridine, etc., N-vinyl lactams, e.g., N-vinyl pyrrolidone, etc., acrylic acid, methacrylic acid, ot-chloroacrylic acid and salts of these acids, cyclic imides, e.g., vinyl succinimide, vinyl phthalimide, etc., vinyl alkyl ketones, vinyl alkyl ethers, N-vinyl alkyl urethanes wherein in each instance the alkyl group contains from 1-4 carbon atoms, e.g., vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, vinyl methyl ether, vinyl butyl. ether, N-vinyl ethylurethane, N-vinyl butylurethane, etc., vinyl sulfonamides, e.g., vinyl sulfonamide, N-vinyl maleamide, itaconamide, N-rnethyl furnaramide, N,N-di-' ethyl fumaramide, etc., fumaramates, maleamates, itaconamates, citraconamates, ethylene, isobutylene, propylene, and the like. Any amount of comonomers up to 50 percent by weight of the monomeric mixture can be used. However, the preferred proportions are from about 70- percent by weight of acrylonitrile and from 30-5 percent by weight of the comonomer. Thus, the process of the invention has an overall scope of proportions of from 50- percent of acrylonitrile and from 50-0 percent byweight, i.e., up to 50 percent, of at least one other polymerizable monomer. 111 general, the proportions of the substituents in the copolymers are the same as in the starting polymerization reaction mixtures.

The process of the invention can also be carried out with advantage by including various additives in the po lymerization mixtures. Chain transfer agents such as phenols and alkyl mercaptans may be added in amounts of from 0.01-2.0 percent based on the weight of monomer. Pigments for delustering or for coloring fibers and films can be added before polymerization or just before spinning or casting. The process can also be operated in continuous manner wherein the ingredients are added continuously and the resulting polymer solution is continuously withdrawn from the system. Preferably, normal atmospheric pressures are used, but lower or higher than atmospheric pressures are also operable and can be used, if desired.

The following examples serve further to illustrate the manner of practicing the process of the invention.

EXAMPLE 1 One hundred grams of acrylonitrile was mixed with 300 ml. of ethylene carbonate at 35 C. Ten milligrams of cupric chloride and 0.75 g. of potassium persulfate were added and the mixture was stirred under a nitrogen atmosphere for 4 hours. At this time the composition of the resultant viscous solution was found to be 97 g. of polyacrylonitrile with an intrinisic viscosity of 2.65. This solution was clear and substantially colorless. Fibers were made using a wet-spinning procedure. These fibers were nearly white and had a tensile strength of 4.10 g./den.

EXAMPLE. 2

One hundred grams of acrylonitrile was mixed with 300 ml. of N,N-dimethylformamide at 45 C. Forty milligrams of cupric chloride and 1.5 g. of potassium persulfate was added and the mixture was stirred for 5 hours under a nitrogen atmosphere. A viscous solution was the result at this time and analysis showed a 92.3 percent conversion of the acrylonitrile monomer to polymer. This solution was clear and substantially colorless. Fibers were spun from this solution by extruding the solution into a heated chamber. The resulting fibers were drafted and heat-set. Th3 properties of these fibers. are listed in the following ta e.

Color, essentially white.

Flow point C 210-220 EXAMPLE 3 Three hundred grams of acrylonitrile was polymerized in 900 ml. of N,N-dimethylformamide using 120 mg. of cupric nitrate, 4.5 g. of potassium persulfate, and the conditions described in Example 2. The resulting viscous solution was divided into two parts. One part was converted to fibers by a wet-spinning technique. The fibers had the following properties:

Color, white.

Strength g./den.. 4.3 Denier 4 Elongation Percent 14.2 Sticking temp. C 233-238 Flow point C 220-225 The remaining portion of the solution was converted into films of polyacrylonitrile by spreading the solution on metal plates at :80-150 C. These films were colorless or had a very light straw color. The films could be drafted to give tough, flexible films.

EXAMPLE 4 Ninety-three grams of acrylonitrile, 7 g. of methyl acrylate, and 300 ml. of dimethyl sulfoxide were mixed at 20 C. Five milligrams of cupric chloride and 0.75 g. of Caros acid (H SO were added and the mixture was stirred under a nitrogen atmosphere for 3.5 hours. After this time a viscous solution was observed to contain 97.5 g. of polymer having an intrinsic vicosity of 2.68. The solution was essentially colorless and could be converted into films or fibers by solvent extraction using water or mixtures of water and water-miscible organic liquids.

EXAMPLE 5 Using the technique described in Example 4, the same polymer composition was prepared in -butyrolactone. This polymer had similar properties and could be converted to films and fibers by the same method.

EXAMPLE 6 Ninety-three grams of acrylonitrile, 7 g. of ethyl acrylate, and 400 ml. of ethylene carbonate were mixed together. One gram of finely divided titanium dioxide, 0.5 g. of t-dodecyl-mercaptan, 25 mg. of cupric chloride, and 0.75 g. of potassium persulfate were added and this mixture was then stirred under a nitrogen atmosphere for 4.5 hours. After this time analysis showed a 96.5 percent conversion of the monomers to polymer which had the composition 93 percent acrylonitrile and 7 percent ethyl acrylate units.

EXAMPLE 7 Eighty grams of acrylonitrile, 20 g. of N,N-dimethylacrylamide, and 300 g. of N,N-dimethylacetamide were mixed together. One gram of finely divided titanium dioxide, mg. of cupric chloride, and 1.2 g. of potassium persulfate were added and this mixture was stirred for 3.5 hours at 40 C. The resulting polymer solution was spun into fibers using a wet-spinning technique. The fibers had excellent strength properties and dyed well with acetate and acid wool dyes.

EXAMPLE 8 Ninety-three grams of acrylonitrile, 4 g. of methyl acrylate, and 3 g. of sodium a'llyl sulfonate were mixed with 300 ml. of ethylene carbonate which contained 16 mg. of finely divided copper metal and 0.5 g. of potassium persulfate. This mixture was stirred at 30 C. under a nitrogen atmosphere for 5 hours. A viscous solution of the terpolyrner composed of 93 percent acrylonitrile, 4 percent methyl acrylate and 3 percent sodium sulfonate was obtained. This polymer was spun into fibers using a wet-spinning technique. These fibers dyed well with basic dyes.

tion was clear and substantially colorless. Fibers were made using a wet-spinning procedure. These fibers were nearly white and had a tensile strength of 4.10 g./ den.

EXAMPLE 10 One hundred grams of acrylonitrile was mixed with 300 ml. of N,N-dimethylformamide at 45 C. 40 mg. of ruthenium chloride and 1.5 g. of potassium persulfate were added and the mixture was stirred for 5 hr. under a nitrogen atmosphere. A viscous solution was the result at this time and analysis showed a 92.3% conversion of the acrylonitrile monomer to polymer. This solution was clear and substantially colorless. Fibers were spun from this solution by extruding the solution into a heated chamber. The resulting fibers were drafted and heat-set. The prop erties of these fibers are listed in the following table.

Color, essentially white.

Strength g./den 3.88

Denier 10 Elongation Percent 16.3

Sticking temp. C 235-242 Flow point C 210-220 EXAMPLE 11 Three hundred grams of acrylonitrile was polymerized in 900 ml. of N,N-dimethylformamide using 120 mg. of ruthenium nitrate, 4.5 g. of potassium persulfate, and the condition described in Example 10. The resulting viscous solution was divided into 2 parts. One part was converted to fibers by a wet-spinning technique. The fibers had the following properties:

Color, White.

Strength g./den 4.3 Denier 4 Elongation Percent 14.2 Sticking temp. C 233-238 Flow point C 220-225 The remaining portion of the solution was converted into films of polyacrylonitrile by spreading the solution on metal plates at -150 C. These films were colorless or had a very light straw color. The films could be drafted to give tough, flexible films.

EXAMPLE 12 EXAMPLE 13 Using the technique described in Example 12, the same polymer composition was prepared in y-butyrolactone. This polymer had similar properties and could be converted to films and fibers by the same method.

EXAMPLE 14 Ninety-three g. of acrylonitrile, 7 g. of ethyl acrylate, and 400 ml. of ethylene carbonate were mixed together.

1 g. of finely divided titanium dioxide, 0.5 g. of t-dodecylmercaptan, 25 mg. of ruthenium chloride, and 0.75 g.

of potassium persulfate were added and this mixture was then stirred under a nitrogen atmosphere for 4.5 hr. After this time analysis showed a 96.5% conversion of the monomers to polymer which had the composition 93% acrylonitrile and 7% ethyl acrylate units.

EXAMPLE Eighty grams of acrylonitrile, g. of N,N-dimethylacrylamide, and 300 g. of N,N-dimethylacetamide were mixed together. 1 g. of finely divided titanium dioxide, 10 mg. of ruthenium chloride, and 1.2 g. of potassium persulfate were added and this mixture was stirred for 3.5 hr. at 40 C. The resulting polymer solution was spun into fibers using a wet-spinning technique. The fibers had excellent strength properties and dyed well with acetate and acid Wool dyes.

EXAMPLE 16 Ninety-three grams of acrylonitrile, 4 g. of methyl acrylate, and 3 g. of sodium allyl sulfoacetate were mixed with 300 ml. of ethylene carbonate which contained 16 mg. of finely divided ruthenium metal and 0.5 g. of potassium persulfate. This mixture was stirred at 30 C. under a nitrogen atmosphere for 5 hr. A viscous solution of the terpolymer composed of 93% acrylonitrile, 4% methyl acrylate and 3% sodium sulfoacetate was obtained. This polymer was spun into fibers using a wetspinning technique. These fibers dyed well with basic dyes.

By substituting in the preceding examples other of the comonomers that were mentioned as suitable in like amount or in any amount within the specified range of up to 50 percent of comonomer, for example, with methacrylonitrile to give copolymers of acrylonitrile and methacrylonitrile, with 4-vinylpyridine to give copolymers of acrylonitrile with styrene, with N-vinyl pyrrolidone to give copolymers of acrylonitrile and N-vinyl pyrrolidone, etc., similar solutions are obtained which likewise can be directly coated or spun into shaped articles of excellent physical properties.

Although we do not wish to be bound to any particular theory it is believed that the presence of the metal component of the catalyst serves to lower the activation energy for the initiation of a particular polymer chain. We also believe that the lowered energy requirement is a result of an association or complex formation between the monomer molecule and the metal atom or ion. We further believe that larger quantities of these metals in relation to the monomer molecules may afiect the nature of the polymer produced. However, the quantities described in this invention do not result in polymers which have significantly modified properties as compared to the same polymer compositions prepared with more conventional catalysts in water systems.

Another important advantage of the process of the invention is that the presence of the mentioned metallic copper and salts thereof or metallic ruthenium or salts of ruthenium thereof as catalysts permits the reduction of the amount of oxidizing agent and in the total amount of catalyst residues in the final polymeric article. This reduction in residues is important because larger amounts of residual salts must be removed by filtration of the polymer which in a practical process adds to the time and expense of processing the polymer.

The new process of the invention has many advantages. The polymer is obtained as a solution suitable for direct spinning to fibers and filaments or direct coating to films, sheets and other shaped articles. This capability eliminates many laborious and time-consuming steps as compared, for example, to previously proposed processes employing aqueous or other nonsolvent reaction media wherein is involved (1) precipitation of emulsified polymer, (2) filtering and washing of polymer cake, (3) drying polymer, (4) dissolving the polymer and (5) filtering the polymer solution before the final product can be used.

However, the process of the invention is particularly advantageous primarily because of the catalyst system employed therein. We have found that copper and ruthenium containing catalysts in combination with certain oxidizing agents, are highly efficacious for solution polymerization of acrylonitrile. The catalyst can be used in the form of finely divided metallic copper or in the form of various copper salts. The presence of this catalyst system permits the polymerization reaction with acrylonitrile to be carried out smoothly to high-molecular weight products at relatively low temperatures and in a minimum period of time. This is in marked contrast to previously known processes which produce polymers of acrylonitrile in solvents for the polymer wherein relatively long reaction periods are necessary and the resulting polymers are obtained as low yields of low molecular weight polymer which are frequently undesirably colored.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as hereinabove described and as defined in the appended claims.

What we claim is:

1. A process for preparing an acrylontrile polymer which comprises polymerizing acrylonitrile in an organic liquid which is a solvent for polyacrylonitrile, at a temperature of from 70 to C., in the presence of at least about 0.0001 to 3.0 percent of a polyvalent metal selected from the group consisting of copper and about 0.025 to 2.0 percent by weight of monomer of ruthenium and an oxidizing agent selected from the group consisting of monoperoxysulfuric acid, peroxydisulfuric acid, ammonium salt or monoperoxysulf-uric acid, ammonium salt of eroxydisnlfuric acid, an alkali metal salt of monoperoxysulfuric acid, an alkali metal salt of peroxydisulfuric acid and sulfur tetroxide in combination with water.

2. The process of claim 1 carried out in a continuous manner.

3. A process for preparing a solution of polyacrylonitrile which can be used directly to make shaped articles which comprises polymerizing acrylonitrile in N,N-dimethylformamide, at a temperature of from 20-50 C., with from 0.001-1 percent of cupric chloride based on the weight of said acrylonitrile, and from 0.025-2 percent of potassium persulfate based on the weight of said acrylonitrile.

4. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 50100 percent by weight of acrylonitrile and up to 50 percent by weight to make a total of 100 percent of an alkyl acrylate wherein the said alkyl group contains from 1-10 carbon atoms, in ethylene carbonate, at a temperature of from 20-50 C., with from 0.001-1 percent of cupric chloride based on the weight of said monomeric material, and from 0.025-2 percent of potassium persulfate based on the weight of said monomeric material.

5. A process for preparing a solution of acrylonitrile polymer which can e used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 50-100 percent of acrylonitrile and up to 50 percent by weight to make a total of 100 percent of an alkyl acrylate wherein the said alkyl group contains from 1-10 carbon atoms, in dimethylsulfoxide, at a temperature of from 20-50 C., with from 0.001-1 percent of cupric chloride based on the weight of said monomeric material, and from 0.025-2 percent of monoperoxysulfuric acid based on the weight of said monomeric material.

6. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 50-100 percent by weight of acrylonitrile and up to 50 percent by weight to make a total of 100 percent of an alkyl acrylate admixed with an alkali metal salt of an allyl sulfonate, wherein the said alkyl group contains from l-lO carbon atoms, in ethylene carbonate, at a temperature of from -50 C., with from 0.001-1 percent of cupric chloride based on the Weight of said monomeric material, and from 0.025-2 percent of potassium persulfate based on the weight of said monomeric material.

7. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 50-100 percent by weight of acrylonitrile and up to 50 percent to make a total of 100 percent of an N-al-kyl substituted acrylamide wherein the said alkyl group contains from 1-4 carbon atoms, in N,N-di methylacetamide, at a temperature of from 20-50 C., with from 0.001-1 percent of cupric chloride based on the weight of said monomeric material and from 0.025-2 percent of potassium persulfate based on the weight of said monomeric material.

8. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 70-95 percent by weight of acrylonitrile and from -5 percent by weight of ethyl acrylate, in ethylene carbonate, at a temperature of from 20-50" C., with from 0.001-1 percent of cupric chloride based on the weight of said monomeric material, and from 0.025-2 percent of potassium persulfate based on the weight of said monomeric material.

9. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material of from 70-95 percent by Weight of acrylonitrile and from 30-5 percent by weight of methyl acrylate, in dimethylsulfoxide, at a temperature of from 20-50 C., with from 0.001-1 percent of cupric chloride based on the weight of said monomeric material, and from 0.025- 2 percent of monoperoxysulfuric acid based on the weight of said monomeric material.

10. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 70-95 percent by Weight of acrylonitrile and from 30-5 percent by weight of a mixture of methyl acrylate and sodium allyl sulfonate, in ethylene carbonate, at a temperature of from 20-50 C., with from 0.001-1 percent of finely divided copper metal based on the weight of said monomeric material, and from 0.025- 2 percent of potassium persulfate based on the weight of said monomeric material.

11. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 70-95 percent by weight of acrylonitrile and from 30-5 percent by weight of N,N-dimethylacrylamide, in N,N-dimethylacetamide, at a temperature of from 20-50 C., with from 0.001-1 percent of cupric chloride based on the weight of said monomeric material, and from 0.025-2 percent of potassum persulfate based on the weight of said monomeric material.

12. A process for preparing a solution of polyacrylonitrile which can be used directly to make shaped articles which comprises polymerizing acrylonitrile in N,N-dimethylformamide, at a temperature of from 2050 C., with from 0.00l-l% of ruthenium chloride based on the weight of said acrylonitrile, and from 0.025-2% of potassium persulfate based on the weight of said acrylonitrile.

13. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from -100% by weight of acrylonitrile and up to 50% by weight to make a total of of an alkyl acrylate wherein the said alkyl group contains from 1-'10 carbon atoms, in ethylene carbonate, at a temperature of from 20-50 C., with from 0.001-l% of ruthenium chloride based on the weight of said monomeric material, and from 0.025-2% of potassium persulfate based on the weight of said monomeric material.

14. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 50-100% of acrylonitrile and up to 50% by weight to make a total of 100% of an alkyl acrylate wherein the said alkyl group contains from 1-10 carbon atoms, in dimethylsulfoxide, at a temperature of from 20-50 C., with from 0.00l-1% of ruthenium chloride based on the weight of said monomeric material, and from 0.025-2% of monoperoxysulfuric acid based on the weight of said monomeric material.

15. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 50-100% by weight of acrylonitrile and up to 50% by weight to make a total of 100% of an alkyl acrylate admixed with an alkali metal salt of an allyl sulfonate, wherein the said alkyl group contains from l-lO carbon atoms, in ethylene carbonate, at a temperature of from 2050 C., With from 0.00l-1% of ruthenium chloride based on the Weight of said monomeric material, and from 0.0252% of potassium persulfate based on the weight of said monomeric material.

16. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 50-100% by weight of acrylonitrile and up to 50% to make a total of 100% of an N-alkyl substituted acrylamide wherein the said alkyl group contains from 1-4 carbon atoms, in N,N-dimethylacetamide, at a temperature of from 20-50 C., with from 0.001- l% of ruthenium chloride based on the weight of said monomeric material and from 0.025-2% of potassium persulfate based on the weight of said monomeric material.

17. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 70-95% by weight of acrylonitrile and from 30-5% by weight of ethyl acrylate, in ethylene carbonate, at a temperature of from 20-50 C., with from 0.00l-1% of ruthenium chloride based on the weight of said monomeric material, and from 0.0252% of potassium persulfate based on the weight of said monomeric material.

18. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material of from 70-95% by weight of acrylonitrile and from 30-5 by weight of methyl acrylate, in dimethylsulfoxide, at a temperature of from 20-50" C., with from 0.00l-1% of ruthenium chloride based on the weight of said monomeric material, and from 0.025-2% of monoeroxysulfuric acid based on the weight of said monomeric material.

19. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 70-95% by weight of acrylonitrile and from 30-5 by weight of a mixture of methyl acrylate and sodium allyl sulfonate, in ethylene carbonate, at a temperature of from 20-50 C., with from 0.001- 1% of finely divided ruthenium metal based on the weight of said monomeric material, and from 0.025-2% of potassium persulfate based on the weight of said monomeric material.

20. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 7095% by weight of acrylonitrile and from 305% by weight of -N,N-dimethylacrylamide, in N,N-dimethylacetamide, at a temperature of from 2050 C., with from 0.001l% of ruthenium chloride based on the weight of said monomeric material, and from 0.0252% of potassium persulfate based on the weight of said monomeric material.

21. A process for preparing a solution of acrylonitrile polymer which can be used directly to make shaped articles which comprises polymerizing monomeric material consisting of from 50-100% by weight of acrylonitrile and up to 50% by Weight to make a total of 100% of at least one other monoethylenically unsaturated, polymerizable compound containing a single CH =C group, in an organic liquid which is a solvent for polyacrylonitrile, at a temperature of from 70 to 100 C., in the presence of from about 0.0001 to about 3.0% by weight based on monomer weight of a polyvalent metal selected from the group consisting of copper and ruthenium and salts of said metals and (2) from about 0.025 to about 2.0% based on monomer weight of an oxidizing agent selected from the group consisting of monoperoxysull2 furic acid, peroxydisulfuric acid, ammonium salt of mouoperoxysulfuric acid, ammonium salt of peroxydisulfuric acid, an alkali metal salt of monoperoxysulfuric acid, an alkali metal salt of peroxydisulfuric acid and sulfur tetroxide in combination with water.

References Cited UNITED STATES PATENTS 2,768,148 10/1956 Schildknecht et al. 260-88.7 2,794,793 6/1957 Coover 26088.7 2,858,290 10/1958 Davis et al. 260-308 3,020,265 2/1962 Tietz 260-88.7 3,060,157 10/1962 Goodman et al. 26085.5 3,069,402 12/1962 Smart 26085.5 3,145,194 8/1964 Heckmaier 26088.7

FOREIGN PATENTS 1,040,242 10/ 1958 Germany.

MORRIS LIEBMAN, Primary Examiner.

B. A. AMERNICK, Assistant Examiner. 

21. A PROCESS FOR PREPARING A SOLUTION OF ACRYLONITRILE POLYMER WHICH CAN BE USED DIRECTLY TO MAKE SHAPED ARTICLES WHICH COMPRISES POLYMERIZING MONOMERIC MATERIAL CONSISTING OF FROM 50-100% BY WEIGHT OF ACRYLONITRILE AND UP TO 50% BY WEIGHT TO MAKE A TOTAL OF 100% OF AT LEAST ONE OTHER MONOETHYLENICALLY UNSATURATED, POLYMERIZABLE COMPOUND CONTAINING A SINGLE CH2=C<GROUP, IN AN ORGANIC LIQUID WHICH IS A SOLVENT FOR POLYACRYLONITRILE, AT A TEMPERATURE OF FROM -70 TO 100*C., IN THE PRESENCE OF FROM ABOUT 0.0001 TO ABOUT 3.0% BY WEIGHT BASED ON MONOMER WEIGHT OF A POLYVALENT METAL SELECTED FROM THE GROUP CONSISTING OF COPPER AND RUTHENIUM AND SALTS OF SAID METALS AND (2) FROM ABOUT 0.025 TO ABOUT 2.0% BASED ON MONOMER WEIGHT OF AN OXIDIZING AGENT SELECTED FROM THE GROUP CONSISTING OF MONOPEROXYSULFURIC ACID, PEROXYDISULFURIC ACID, AMMONIUM SALT OF MONOPEROXYSULFURIC ACID, AMMONIUM SALT OF PEROXYDISULFURIC ACID, AN ALKALI METAL SALT OF MONOPEROXYSULFURIC ACID, AN ALKALI METAL SALT OF PEROXYDISULFURIC ACID AND SULFUR TETROXIDE IN COMBINATION WITH WATER. 